Liquids

ABSTRACT

The present invention relates to ionic liquid comprising an anion and a cation wherein the cation is a primary, secondary or tertiary ammonium ion containing a protonated nitrogen atom.

The present invention relates to ionic liquids and uses thereof. Theinvention also provides processes for the manufacture of ionic liquids.

Ionic liquids are compounds which are composed of ions but which have amelting point below ambient temperature. They can be formed by asuitable combination of charge-delocalised, desymmetrised ions. Thedegree of order of the resulting salt can be reduced and the meltingpoint lowered to a point where the resultant salt is liquid at ambienttemperature. The delocalisation of the charge on the ion is also animportant factor in determining the melting point of the resulting salt.Ionic liquids possess a number of remarkable properties, includingnegligible vapour pressure and high solvation capabilities, which haverendered them interesting alternatives to conventional solvents in avariety of applications.

Ionic liquids may be made up of anions and cations or alternativelyconsist of zwitterions carrying both a positive and a negative charge onthe same molecule. Most commonly the ionic liquid will comprise an anionand a cation.

The prior art comprises liquids composed of a quaternary nitrogen- orphosphorus-based cation, for example, based on a nucleus selected fromquaternary ammonium cations, pyrrolidinium cations, imidazolium cations,triazolium cations, pyridinium cations, pyridazinium cations,pyrimidinium cations, pyrazinium cations and triazinium cations. Thesetypes of ionic liquids tend to be highly viscous, potentially hazardousand strongly absorb UV and visible light. Furthermore, the preparationof these ionic liquids involves a number of chemical and chromatographicsteps that makes the process time consuming, expensive and inefficient.

Anderson et al., J. Am. Chem. Soc. 124:14247-14254 (2002) disclosesionic liquids composed of a primary or tertiary ammonium based cationfor use in certain chemical applications.

The inventors have provided further ionic liquids.

According to the present invention there is provided an ionic liquidcomprising an anion and a cation wherein the cation is a primary,secondary or tertiary ammonium ion containing a charged nitrogen atom.

As used herein a “primary ammonium ion” is an ammonium ion in which thenitrogen has 1 carbon atom attached to it.

As used herein a “secondary ammonium ion” is an ammonium ion in whichthe nitrogen has 2 carbon atoms attached to it.

As used herein a “tertiary ammonium ion” is an ammonium ion in which thenitrogen has 3 carbon atoms attached to it.

According to a further aspect of the present invention there is providedan ionic liquid comprising an anion and a cation characterised in thatthe cation is a nitrogen-containing cation of the formula (I)N⁺HRR′R″  (I)in which R is a hydrocarbyl group optionally substituted with by one ormore substituents selected from nitrogen-containing functional groups(including nitrile, nitro or amino or another basic nitrogen-containingfunctional group), thiol, alkythio, sulphonyl, thiocyanate,isothiocyanate, azido, hydrazino, halogen, alkyl optionally interruptedby one or more ether or thioether linkages, alkoxy, alkenyl, hydroxy,carbonyl (including aldehyde or ketone), carboxyl, boronate, silyl andsubstituted amino (e.g. mono- or di-alkylamino or alkyamido); and

-   R′ and R″, which may be the same or different, each represent H or    R; or any two or three of R, R′ and R″ may be joined together with    the N to form a cyclic group.

The term “ionic liquid” herein includes, but is not limited to,compounds consisting of ions and liquid at temperatures at which thecompound is stable and the ionic liquids may have a melting point below100° C., for example, below 25° C. and optionally below 20° C. Theboiling point of the ionic liquid may be at least 200° C. It may beabove 500° C. or even above 1000° C.

The ionic liquids of the invention may consist entirely of ions, whichare liquid at the previously above defined temperatures in the drystate. Such ionic liquids will generally contain less than 1% water,preferably less than 1000 ppm water and more preferably still less than100 ppm water by mass.

In a preferred aspect of the invention, ionic liquids are defined ascompounds consisting of a cation and an anion and having a water contentof less than 100 parts per million. Preferably still, the ionic liquidshave a melting point of 30° C. or below, and a viscosity of less than500 centipoise.

For the purposes of this invention hydrocarbyl includes, but is notlimited to, alkyl, alkenyl, alkynyl, cyclohydrocarbyl, for examplecycloalkyl, cycloalkenyl and moieties containing a combination thereof.

As used herein “alkyl” relates to both straight chain and branched alkylradicals, for example, of 1 to 12 carbon atoms, e.g. 1, 2, 3, 4, 5, 6,7, 8 carbon atoms including but not limited to methyl, ethyl, n-propyl,isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl,n-heptyl, n-octyl. The term alkyl also encompasses cycloalkyl radicalsincluding but not limited to cyclopropyl, cyclobutyl, cyclopentyl orcyclohexyl.

The alkyl group may be substituted with one or more halogen atoms. Inone class of compounds the halogen is fluorine, in another it ischlorine, in a third it is a combination of fluorine and chlorine.

“Alkoxy” relates to both straight chain and branched alkyl radicals, forexample, of 1 to 12 carbon atoms, e.g. 1, 2, 3, 4, 5, 6, 7, 8 carbonatoms containing one or more oxygen atoms or hydroxyl.

The term “alkenyl” means a straight or branched alkenyl radical of, forexample, 2 to 12 carbon atoms, such as 2, 3, 4, 5 or 6 carbon atoms, andcontaining one or more carbon-carbon double bonds and includes but isnot limited to ethylene, n-propyl-1-ene, n-propyl-2-ene, isopropyleneetc.

“Alkynyl” relates to a straight or branched alkynyl radical of, forexample, 2 to 12 carbon atoms, such as 2, 3, 4, 5 or 6 carbon atoms, andcontaining one or more triple bonds.

“Cyclohydrocarbyl” relates to a saturated, partly unsaturated orunsaturated 3-10, for example, 5, 6, 7, 8, 9 or 10, membered hydrocarbonring, including cycloalkyl or aryl.

“Aryl” means an aromatic, for example, 6-10 membered hydrocarboncontaining one, e.g. 6C-10C, ring which is optionally fused to one ormore saturated or unsaturated rings, including phenyl or phenylsubstituted by an alkyl or alkoxy group in which alkyl and alkoxy are asdescribed herein.

“Heteroaryl” means an aromatic, for example, 5-10 membered aromatic ringcontaining one or more heteroatoms selected from N, O or S, andcontaining one ring which is optionally fused to one or more saturatedor unsaturated rings.

“Heterocyclyl” means, for example, a 3-10 membered ring systemcontaining one or more heteroatoms selected from N, O or S and includesheteroaryl. The heterocyclyl system may contain one ring or may be fusedto one or more saturated or unsaturated rings; the heterocyclyl may befully saturated, partially saturated or unsaturated.

“Cyclic group” means a ring or ring system, which may be unsaturated orpartially unsaturated but is usually saturated, typically containing 5to 13 ring-forming atoms, for example a 5- or 6-membered ring. Examplesinclude cyclohydrocarbyl or heterocyclyl.

Examples of cyclohydrocarbyl or heterocyclyl groups include but are notlimited to cyclohexyl, phenyl, acridine, benzimidazole, benzofuran,benzothiophene, benzoxazole, benzothiazole, carbazole, cinnoline,dioxin, dioxane, dioxolane, dithiane, dithiazine, dithiazole,dithiolane, furan, imidazole, imidazoline, imidazolidine, indole,indoline, indolizine, indazole, isoindole, isoquinoline, isooxazole,isothiazole, morpholine, napthyridine, oxazole, oxadiazole, oxathiazole,oxathiazolidine, oxazine, oxadiazine, phenazine, phenothiazine,phenoxazne, phthalazine, piperazine, piperidine, pteridine, purine,putrescine, pyran, pyrazine, pyrazole, pyrazoline, pyrazolidine,pyridazine, pyridine, pyrimidine, pyrrolidine, pyrrole, pyrroline,quinoline, quinoxaline, quinazoline, quinolizine, tetrahydrofuran,tetrazine, tetrazole, thiophene, thiadiazine, thiadiazole, thiatriazole,thiazine, thiazole, thiomorpholine, thianaphthalene, thiopyran,triazine, triazole, trithiane, tropine.

Halogen means F, Cl, Br, or I.

In one class of compounds R′ and R″ are H. Compounds such as thesehaving 1 R group and 3 hydrogens are referred to herein as primaryammonium ions.

The invention covers compounds of formula (I) having 2 R groups and 2hydrogens and which are referred to herein as secondary ammonium ionsrespectively. The invention further covers compounds having 3 R groupsand 1 hydrogen and which are referred to herein as tertiary ammoniumions.

Included is a class of compounds in which R′ and R″ are different andhave the same meaning as R.

In a preferred aspect of the invention there is provided an ionic liquidconsisting of an anion and a cation as defined in the first aspect ofthe invention.

In a preferred aspect of the invention the cyclic group is acyclohydrocarbyl or hetereocyclyl group, for example cyclohexylammonium.

In one class of compounds there are excluded cations wherein any two orthree of R, R′, R″ may be joined together with the N to form an aryl orheteroaryl group. Specifically excluded are pyridinium, pyrrolidiniumand imidazolium cations. In one class of compounds where R isunsubstituted, there are excluded cations where R, R′and R″ are the sameand are ethyl or butyl.

In one class of compounds wherein R, R′ and/or R″ is an unsubstitutedhydrocarbyl group, the invention may include the following provisos:

Where R is ethyl, the invention may include the proviso that R′ and/orR″ are not H.

Where R′ and R″ are both CH₃, the invention may include the proviso thatR is not H.

Where one or R′ and R″ is H and the other is CH₃, the invention mayinclude the proviso that R is not CH₃.

The invention may include the proviso that the ionic liquid is not anyof the following:

-   Ethylammonium nitrate-   Tributylammonium-acetate-   Tributylammoniumα-cyano-4-hydroxycinnamate-   Tributylammonium sinapate-   Dimethylammonium pyridine-2-carboxylate-   Tributylammonium pyridine-2-carboxylate-   Tributylammonium 3-hydroxypyridine-2-carboxylate-   Triethylammonium pyridine-2-carboxylate

In addition to demonstrating high solvation capability, the ionicliquids of the present invention have a low viscosity, are non-toxic andare colourless. These features make the ionic liquids of the presentinvention useful in a variety of applications.

Preferably, R is substituted with a moiety selected from the groupconsisting of alkenyl, hydroxyl, amino, thio, carbonyl and carboxylgroups. More preferably, R is substituted with a hydroxyl or aminogroup.

In one class of compounds, where R is substituted with a hydroxyl group,the invention may include the proviso that the ionic liquid is notdiethanolammonium chloride.

If more than one substituent group (for example, selected from the groupconsisting of alkenyl, hydroxyl, amino, thiol, carbonyl and carboxylgroups) is present then more than one substituent group may be presenton a single cation.

In one class of compounds, R is a hydroxyalkyl group having 1, 2, 3, 4,5 or 6 C atoms. The hydroxyalkyl group may have a hydroxyl moiety on itsfree, terminal carbon. R may be a polyol having 2 to 6 C atoms, forexample, a di-alkanol, tri-alkanol or tetra-alkanol group.

Preferably, the cation is an ethanolammonium, N-(alkoxyethyl)ammonium,N-methylethanolammonium, N,N-dimethylethanolammonium, diethanolammonium,N-alkyldiethanolammonium (e.g butyldiethanolammonium),N,N-di(alkoxyalkyl)ammonium (e.g di(methoxyethyl)ammonium) ortriethanolammonium ion.

More preferably the cation is a methylethanolammonium, N,Ndimethylethanolammonium, N, N-di(methoxyethyl)ammonium) orbutyldiethanolammonium ion.

In another class of compounds, R is an aminoalkyl group having 2 to 8 Catoms, for example, 2, 3, 4, 5, 6, 7 or 8 C atoms. The aminoalkyl may bea di or tri-aminoalkyl group.

In some compounds, R is putrescine, piperidine, or tropine.

Preferred cations include an ethanolammonium, diethanolammonium,N-butyldiethanolammonium, N-methylethanolammonium,di(methoxyethyl)ammonium, N,N-dimethylethanolammonium, putrescinium,1-(3-hydroxypropyl)putrescinium, orN-(3-hydroxypropyl)-N-methylcyclohexylammonium ion. Preferably still,cations include N-butyldiethanolammonium, N-methylethanolammonium,di(methoxyethyl)ammonium, N,N-dimethylethanolammonium, putrescinium,1-(3-hydroxypropyl)putrescinium, orN-(3-hydroxypropyl)-N-methylcyclohexylammonium ion.

Any cation included in the above list may be combined with any disclosedanion.

The identity of the anions in the ionic liquids of the invention is notcritical. The only theoretical constraint upon the choice of the anionis its ionic weight in order to keep the melting point of the ionicliquid below the desired temperature.

Preferably the anion is selected from halogenated inorganic anions,nitrates, sulphates, phosphates, carbonates, sulphonates andcarboxylates. The sulphonates and carboxylates may be alkylsulphonatesand alkylcarboxylates, in which the alkyl group is a moiety, for examplehaving 1 to 20 C atoms, selected alkyl and alkyl substituted at anyposition with alkenyl, alkoxy, alkeneoxy, aryl, arylalkyl, aryloxy,amino, aminoalkyl, thio, thioalkyl, hydroxyl, hydroxyalkyl, carbonyl,oxoalkyl, carboxyl, carboxyalkyl or halide function, including allsalts, ethers, esters, pentavalent nitrogen or phosphorus derivatives orstereoisomers thereof. For example, the anion may be selected frombis(trifluoromethylsulphonyl)imide, carbonate, hydrogen carbonate,sulphate, hydrogen sulphate, silicate, phosphate, hydrogen phosphate,dihydrogen phosphate, metaphosphate, methanesulphonate,trifluoromethanesulphonate, ethylenediaminetetraacetate, chloride,bromide, iodide, hexafluorophosphate, tetrafluoroborate,trifluoroacetate, pentafluoropropanoate, heptafluorobutanoate, oxalate,formate, acetate, propanoate, butanoate, pentanoate, hexanoate,heptanoate, octanoate, nonanoate, decanoate, benzoate,benezenedicarboxylate, benzenetricarboxylate, benzenetetracarboxylate,chlorobenzoate, fluorobenzoate, pentachlorobenzoate, pentafluorobenzoatesalicylate, glycolate lactate, pantothenate, tartrate, hydrogentartrate, mandelate, crotonate, malate, pyruvate, succinate, citrate,fumarate, phenylacetate. An especially preferred anion is an organiccarboxylate. When the anion is required to include a labile proton thenglycolate, tartrate and lactate anions are preferred. These contain bothacid and hydroxyl functional groups.

The ionic liquid according to the invention may contain cations whichare all the same or which are different. In the same way, the ionicliquids may contain anions which are all the same or which aredifferent. Thus the invention encompasses ionic liquids including amixture of different cations and/or different anions.

Ionic liquids of the invention may include any of the following:

-   Ethanolammonium formate-   Ethanolammonium acetate-   Ethanolammonium propanoate-   Ethanolammonium propanedioate-   Ethanolammonium butanoate-   Ethanolammonium butenoate-   Ethanolammonium butanedioate-   Ethanolammonium pentanoate-   Ethanolammonium pentanedioate-   Ethanolammonium pentenoate-   Ethanolammonium hexanoate-   Ethanolammonium hexanedioate-   Ethanolammonium hexenoate-   Ethanolammonium heptanoate-   Ethanolammonium heptanedioate-   Ethanolammonium heptenoate-   Ethanolammonium octanoate-   Ethanolammonium octanedioate-   Ethanolammonium octenoate-   Ethanolammonium nonanoate-   Ethanolammonium nonanedioate-   Ethanolammonium nonenoate-   Ethanolammonium decanoate-   Ethanolammonium decanedioate-   Ethanolammonium decenoate-   Ethanolammonium undecanoate-   Ethanolammonium undecanedioate-   Ethanolammonium undecenoate-   Ethanolammonium dodecanoate-   Ethanolammonium dodecanedicarboxylate-   Ethanolammonium dodecenecarboxylate-   Ethanolammonium cyclohexanecarboxylate-   Ethanolammonium cyclohexenecarboxylate-   Ethanolammonium phenoxide-   Ethanolammonium benzoate-   Ethanolamnonium benezenedicarboxylate-   Ethanolammonium benzenetricarboxylate-   Ethanolammonium benzenetetracarboxylate-   Ethanolammonium chlorobenzoate-   Ethanolammonium fluorobenzoate-   Ethanolammonium pentachlorobenzoate-   Ethanolammonium pentafluorobenzoate-   Ethanolammonium salicylate-   Ethanolammonium glycolate-   Ethanolammonium lactate-   Ethanolammonium pantothenate-   Ethanolammonium tartrate-   Ethanolammonium hydrogen tartrate-   Ethanolammonium mandelate-   Ethanolammonium crotonate-   Ethanolammonium malate-   Ethanolammonium pyruvate-   Ethanolammonium succinate-   Ethanolammonium citrate-   Ethanolammonium fumarate-   Ethanolammonium phenylacetate-   Ethanolammonium oxalate-   Ethanolammonium bis(trifluoromethylsulphonyl)imide-   Ethanolammonium carbonate-   Ethanolammonium hydrogen carbonate-   Ethanolammonium sulphate-   Ethanolammonium hydrogen sulphate-   Ethanolammonium phosphate-   Ethanolammonium hydrogen phosphate-   Ethanolammonium dihydrogen phosphate-   Ethanolammonium methanesulfonate-   Ethanolammonium trifluoromethanesulphonate-   Ethanolammonium ethylenediaminetetraacetate-   Ethanolammonium hexafluorophosphate-   Ethanolammonium tetrafluoroborate-   Ethanolammonium trifluoroacetate-   Ethanolammonium pentafluoropropanoate-   Ethanolammonium heptafluorobutanoate-   Ethanolammonium phosphoenolpyruvate-   Ethanolammonium nicotinamide adenine dinucleotide phosphate-   Ethanolammonium adenosinephosphate-   Ethanolammonium adenosine diphosphate-   Ethanolammonium adenosine triphosphate-   Ethanolammonium oxyniacate-   Ethanolammonium nitrate-   Ethanolammonium nitrite-   Diethanolammonium bromide-   Diethanolammonium iodide-   Diethanolammonium formate-   Diethanolammonium acetate-   Diethanolammonium propanoate-   Diethanolammonium propanedioate-   Diethanolammonium butanoate-   Diethanolammonium butenoate-   Diethanolammonium butanedioate-   Diethanolammonium pentanoate-   Diethanolammonium pentanedioate-   Diethanolammonium pentenoate-   Diethanolammonium hexanoate-   Diethanolammonium hexanedioate-   Diethanolammonium hexenoate-   Diethanolammonium heptanoate-   Diethanolammonium heptanedioate-   Diethanolammonium heptenoate-   Diethanolammonium octanoate-   Diethanolammonium octanedioate-   Diethanolammonium octenoate-   Diethanolammonium nonanoate-   Diethanolammonium nonanedioate-   Diethanolammonium nonenoate-   Diethanolammonium decanoate-   Diethanolammonium decanedioate-   Diethanolammonium decenoate-   Diethanolammonium undecanoate-   Diethanolammonium undecanedioate-   Diethanolammonium undecenoate-   Diethanolammonium dodecanoate-   Diethanolammonium dodecanedicarboxylate-   Diethanolammonium dodecenecarboxylate-   Diethanolammonium cyclohexanecarboxylate-   Diethanolammonium cyclohexenecarboxylate-   Diethanolammonium phenoxide-   Diethanolammonium benzoate-   Diethanolammonium benezenedicarboxylate-   Diethanolammonium benzenetricarboxylate-   Diethanolammonium benzenetetracarboxylate-   Diethanolammonium chlorobenzoate-   Diethanolammonium fluorobenzoate-   Diethanolammonium pentachlorobenzoate-   Diethanolammonium pentafluorobenzoate-   Diethanolammonium salicylate-   Diethanolammonium glycolate-   Diethanolammonium lactate-   Diethanolammonium pantothenate-   Diethanolammonium tartrate-   Diethanolammonium hydrogen tartrate-   Diethanolammonium mandelate-   Diethanolammonium crotonate-   Diethanolammonium malate-   Diethanolammonium pyruvate-   Diethanolammonium succinate-   Diethanolammonium citrate-   Diethanolammonium fumarate-   Diethanolammonium phenylacetate-   Diethanolammonium oxalate-   Diethanolammonium bis(trifluoromethylsulphonyl)imide-   Diethanolammonium carbonate-   Diethanolammonium hydrogen carbonate-   Diethanolammonium phosphate-   Diethanolammonium hydrogen phosphate-   Diethanolammonium dihydrogen phosphate-   Diethanolammonium methanesulphonate-   Diethanolammonium trifluoromethanesulphonate-   Diethanolammonium ethylenediaminetetraacetate-   Diethanolammonium hexafluorophosphate-   Diethanolammonium tetrafluoroborate-   Diethanolammonium trifluoroacetate-   Diethanolammonium pentafluoropropanoate-   Diethanolammonium heptafluorobutanoate-   Diethanolammonium phosphoenolpyruvate-   Diethanolammonium nicotinamide adenine dinucleotide phosphate-   Diethanolammonium adenosinephosphate-   Diethanolammonium adenosine diphosphate-   Diethanolammonium adenosine triphosphate-   Diethanolammonium oxyniacate-   Diethanolammonium nitrate-   Diethanolammonium nitrite-   N-Butyldiethanolammonium chloride-   N-Butyldiethanolammonium bromide-   N-Butyldiethanolammonium iodide-   N-Butyldiethanolammonium formate-   N-Butyldiethanolammonium acetate-   N-Butyldiethanolammonium propanoate-   N-Butyldiethanolammonium propanedioate-   N-Butyldiethanolammonium butanoate-   N-Butyldiethanolammonium butenoate-   N-Butyldiethanolammonium butanedioate-   N-Butyldiethanolammonium pentanoate-   N-Butyldiethanolammonium pentanedioate-   N-Butyldiethanolammonium pentenoate-   N-Butyldiethanolammonium hexanoate-   N-Butyldiethanolammonium hexenoate-   N-Butyldiethanolammonium heptanoate-   N-Butyldiethanolammonium heptanedioate-   N-Butyldiethanolammonium heptenoate-   N-Butyldiethanolammonium octanoate-   N-Butyldiethanolammonium octanedioate-   N-Butyldiethanolammonium octenoate-   N-Butyldiethanolammonium nonanoate-   N-Butyldiethanolammonium nonanedioate-   N-Butyldiethanolammonium nonenoate-   N-Butyldiethanolammonium decanoate-   N-Butyldiethanolammonium decanedioate-   N-Butyldiethanolammonium decenoate-   N-Butyldiethanolammonium undecanoate-   N-Butyldiethanolammonium undecanedioate-   N-Butyldiethanolammonium undecenoate-   N-Butyldiethanolammonium dodecanoate-   N-Butyldiethanolammonium dodecanedicarboxylate-   N-Butyldiethanolammonium dodecenecarboxylate-   N-Butyldiethanolammonium cyclohexanecarboxylate-   N-Butyldiethanolammonium cyclohexenecarboxylate-   N-Butyldiethanolammonium phenoxide-   N-Butyldiethanolammonium benzoate-   N-Butyldiethanolammonium benezenedicarboxylate-   N-Butyldiethanolammonium benzenetricarboxylate-   N-Butyldiethanolammonium benzenetetracarboxylate-   N-Butyldiethanolammonium chlorobenzoate-   N-Butyldiethanolammonium fluorobenzoate-   N-Butyldiethanolammonium pentachlorobenzoate-   N-Butyldiethanolammonium pentafluorobenzoate-   N-Butyldiethanolammonium salicylate-   N-Butyldiethanolammonium glycolate-   N-Butyldiethanolammonium lactate-   N-Butyldiethanolammonium pantothenate-   N-Butyldiethanolammonium tartrate-   N-Butyldiethanolammonium hydrogen tartrate-   N-Butyldiethanolammonium mandelate-   N-Butyldiethanolammonium crotonate-   N-Butyldiethanolammonium malate-   N-Butyldiethanolammonium pyruvate-   N-Butyldiethanolammonium succinate-   N-Butyldiethanolammonium citrate-   N-Butyldiethanolammonium fumarate-   N-Butyldiethanolammonium phenylacetate-   N-Butyldiethanolammonium oxalate-   N-Butyldiethanolammonium bis(trifluoromethylsulphonyl)imide-   N-Butyldiethanolammonium carbonate-   N-Butyldiethanolammonium hydrogen carbonate-   N-Butyldiethanolammonium sulphate-   N-Butyldiethanolammonium hydrogen sulphate-   N-Butyldiethanolammonium phosphate-   N-Butyldiethanolammonium hydrogen phosphate-   N-Butyldiethanolammonium dihydrogen phosphate-   N-Butyldiethanolammonium methanesulphonate-   N-Butyldiethanolammonium trifluoromethanesulphonate-   N-Butyldiethanolammonium ethylenediaminetetraacetate-   N-Butyldiethanolammonium hexafluorophosphate-   N-Butyldiethanolammonium tetrafluoroborate-   N-Butyldiethanolammonium trifluoroacetate-   N-Butyldiethanolammonium pentafluoropropanoate-   N-Butyldiethanolammonium heptafluorobutanoate-   N-Butyldiethanolammonium phosphoenolpyruvate-   N-Butyldiethanolammonium nicotinamide adenine dinucleotide phosphate-   N-Butyldiethanolammonium adenosinephosphate-   N-Butyldiethanolammonium adenosine diphosphate-   N-Butyldiethanolammonium adenosine triphosphate-   N-Butyldiethanolammonium oxyniacate-   N-Butyldiethanolammonium nitrate-   N-Butyldiethanolammonium nitrite-   N,N-Dimethylethanolammonium bromide-   N,N-Dimethylethanolammonium iodide-   N,N-Dimethylethanolammonium formate-   N,N-Dimethylethanolammonium acetate-   N,N-Dimethylethanolammonium propanoate-   N,N-Dimethylethanolammonium propanedioate-   N,N-Dimethylethanolammonium butanoate-   N,N-Dimethylethanolammonium butenoate-   N,N-Dimethylethanolammonium butanedioate-   N,N-Dimethylethanolammonium pentanoate-   N,N-Dimethylethanolammonium pentanedioate-   N,N-Dimethylethanolammonium pentenoate-   N,N-Dimethylethanolammonium hexanoate-   N,N-Dimethylethanolammonium hexenoate-   N,N-Dimethylethanolammonium heptanoate-   N,N-Dimethylethanolammonium heptanedioate-   N,N-Dimethylethanolammonium heptenoate-   N,N-Dimethylethanolammonium octanoate-   N,N-Dimethylethanolammonium octanedioate-   N,N-Dimethylethanolammonium octenoate-   N,N-Dimethylethanolammonium nonanoate-   N,N-Dimethylethanolammonium nonanedioate-   N,N-Dimethylethanolammonium nonenoate-   N,N-Dimethylethanolammonium decanoate-   N,N-Dimethylethanolammonium decanedioate-   N,N-Dimethylethanolammonium decenoate-   N,N-Dimethylethanolammonium undecanoate-   N,N-Dimethylethanolammonium undecanedioate-   N,N-Dimethylethanolammonium undecenoate-   N,N-Dimethylethanolammonium dodecanoate-   N,N-Dimethylethanolammonium dodecanedicarboxylate-   N,N-Dimethylethanolammonium dodecenecarboxylate-   N,N-Dimethylethanolammonium cyclohexanecarboxylate-   N,N-Dimethylethanolammonium cyclohexenecarboxylate-   N,N-Dimethylethanolammonium phenoxide-   N,N-Dimethylethanolammonium benzoate-   N,N-Dimethylethanolammonium benezenedicarboxylate-   N,N-Dimethylethanolammonium benzenetricarboxylate-   N,N-Dimethylethanolammonium benzenetetracarboxylate-   N,N-Dimethylethanolammonium chlorobenzoate-   N,N-Dimethylethanolammonium fluorobenzoate-   N,N-Dimethylethanolammonium pentachlorobenzoate-   N,N-Dimethylethanolammonium pentafluorobenzoate-   N,N-Dimethylethanolammonium salicylate-   N,N-Dimethylethanolammonium glycolate-   N,N-Dimethylethanolammonium lactate-   N,N-Dimethylethanolammonium pantothenate-   N,N-Dimethylethanolammonium tartrate-   N,N-Dimethylethanolammonium hydrogen tartrate-   N,N-Dimethylethanolammonium mandelate-   N,N-Dimethylethanolammonium crotonate-   N,N-Dimethylethanolammonium malate-   N,N-Dimethylethanolammonium pyruvate-   N,N-Dimethylethanolammonium succinate-   N,N-Dimethylethanolammonium citrate-   N,N-Dimethylethanolammonium fumarate-   N,N-Dimethylethanolammonium phenylacetate-   N,N-Dimethylethanolammonium oxalate-   N,N-Dimethylethanolammonium bis(trifluoromethylsulphonyl)imide-   N,N-Dimethylethanolammonium carbonate-   N,N-Dimethylethanolammonium hydrogen carbonate-   N,N-Dimethylethanolammonium sulphate-   N,N-Dimethylethanolammonium hydrogen sulphate-   N,N-Dimethylethanolammonium phosphate-   N,N-Dimethylethanolammonium hydrogen phosphate-   N,N-Dimethylethanolammonium dihydrogen phosphate-   N,N-Dimethylethanolammonium methanesulphonate-   N,N-Dimethylethanolammonium trifluoromethanesulphonate-   N,N-Dimethylethanolammonium ethylenediaminetetraacetate-   N,N-Dimethylethanolammonium hexafluorophosphate-   N,N-Dimethylethanolammonium tetrafluoroborate-   N,N-Dimethylethanolammonium trifluoroacetate-   N,N-Dimethylethanolammonium pentafluoropropanoate-   N,N-Dimethylethanolammonium heptafluorobutanoate-   N,N-Dimethylethanolammonium phosphoenolpyruvate-   N,N-Dimethylethanolammonium nicotinamide adenine dinucleotide    phosphate-   N,N-Dimethylethanolammonium adenosinephosphate-   N,N-Dimethylethanolammonium adenosine diphosphate-   N,N-Dimethylethanolammonium adenosine triphosphate-   N,N-Dimethylethanolammonium oxyniacate-   N,N-Dimethylethanolammonium nitrate-   N,N-Dimethylethanolammonium nitrite-   N-Methylethanolammonium bromide-   N-Methylethanolammonium iodide-   N-Methylethanolammonium formate-   N-Methylethanolammonium acetate-   N-Methylethanolammonium propanoate-   N-Methylethanolammonium propanedioate-   N-Methylethanolammonium butanoate-   N-Methylethanolammonium butenoate-   N-Methylethanolammonium butanedioate-   N-Methylethanolammonium pentanoate-   N-Methylethanolammonium pentanedioate-   N-Methylethanolammonium pentenoate-   N-Methylethanolammonium hexanoate-   N-Methylethanolammonium hexenoate-   N-Methylethanolammonium heptanoate-   N-Methylethanolammonium heptanedioate-   N-Methylethanolammonium heptenoate-   N-Methylethanolammonium octanoate-   N-Methylethanolammonium octanedioate-   N-Methylethanolammonium octenoate-   N-Methylethanolammonium nonanoate-   N-Methylethanolammonium nonanedioate-   N-Methylethanolammonium nonenoate-   N-Methylethanolammonium decanoate-   N-Methylethanolammonium decanedioate-   N-Methylethanolammonium decenoate-   N-Methylethanolammonium undecanoate-   N-Methylethanolammonium undecanedioate-   N-Methylethanolammonium undecenoate-   N-Methylethanolammonium dodecanoate-   N-Methylethanolammonium dodecanedicarboxylate-   N-Methylethanolammonium dodecenecarboxylate-   N-Methylethanolammonium cyclohexanecarboxylate-   N-Methylethanolammonium cyclohexenecarboxylate-   N-Methylethanolammonium phenoxide-   N-Methylethanolammonium benzoate-   N-Methylethanolammonium benezenedicarboxylate-   N-Methylethanolammonium benzenetricarboxylate-   N-Methylethanolammonium benzenetetracarboxylate-   N-Methylethanolammonium chlorobenzoate-   N-Methylethanolammonium fluorobenzoate-   N-Methylethanolammonium pentachlorobenzoate-   N-Methylethanolammonium pentafluorobenzoate-   N-Methylethanolammonium salicylate-   N-Methylethanolammonium glycolate-   N-Methylethanolammonium lactate-   N-Methylethanolammonium pantothenate-   N-Methylethanolammonium tartrate-   N-Methylethanolammonium hydrogen tartrate-   N-Methylethanolammonium mandelate-   N-Methylethanolammonium crotonate-   N-Methylethanolammonium malate-   N-Methylethanolammonium pyruvate-   N-Methylethanolammonium succinate-   N-Methylethanolammonium citrate-   N-Methylethanolammonium fumarate-   N-Methylethanolammonium phenylacetate-   N-Methylethanolammonium oxalate-   N-Methylethanolammonium bis(trifluoromethylsulphonyl)imide-   N-Methylethanolammonium carbonate-   N-Methylethanolammonium hydrogen carbonate-   N-Methylethanolammonium sulphate-   N-Methylethanolammonium hydrogen sulphate-   N-Methylethanolammonium phosphate-   N-Methylethanolammonium hydrogen phosphate-   N-Methylethanolammonium dihydrogen phosphate-   N-Methylethanolammonium methanesulphonate-   N-Methylethanolammonium trifluoromethanesulphonate-   N-Methylethanolammonium ethylenediaminetetraacetate-   N-Methylethanolammonium hexafluorophosphate-   N-Methylethanolammonium tetrafluoroborate-   N-Methylethanolammonium trifluoroacetate-   N-Methylethanolammonium pentafluoropropanoate-   N-Methylethanolammonium heptafluorobutanoate-   N-Methylethanolammonium phosphoenolpyruvate-   N-Methylethanolammonium nicotinamide adenine dinucleotide phosphate-   N-Methylethanolammonium adenosinephosphate-   N-Methylethanolammonium adenosine diphosphate-   N-Methylethanolammonium adenosine triphosphate-   N-Methylethanolammonium oxyniacate-   N-Methylethanolammonium nitrate-   N-Methylethanolammonium nitrite-   N,N-Di(methoxyethyl)ammonium chloride-   N,N-Di(methoxyethyl)ammonium bromide-   N,N-Di(methoxyethyl)ammonium iodide-   N,N-Di(methoxyethyl)ammonium formate-   N,N-Di(methoxyethyl)ammonium acetate-   N,N-Di(methoxyethyl)ammonium propanoate-   N,N-Di(methoxyethyl)ammonium propanedioate-   N,N-Di(methoxyethyl)ammonium butanoate-   N,N-Di(methoxyethyl)ammonium butenoate-   N,N-Di(methoxyethyl)ammonium butanedioate-   N,N-Di(methoxyethyl)ammonium pentanoate-   N,N-Di(methoxyethyl)ammonium pentanedioate-   N,N-Di(methoxyethyl)ammonium pentenoate-   N,N-Di(methoxyethyl)ammonium hexanoate-   N,N-Di(methoxyethyl)ammonium hexenoate-   N,N-Di(methoxyethyl)ammonium heptanoate-   N,N-Di(methoxyethyl)ammonium heptanedioate-   N,N-Di(methoxyethyl)ammonium heptenoate-   N,N-Di(methoxyethyl)ammonium octanoate-   N,N-Di(methoxyethyl)ammonium octanedioate-   N,N-Di(methoxyethyl)ammonium octenoate-   N,N-Di(methoxyethyl)ammonium nonanoate-   N,N-Di(methoxyethyl)ammonium nonanedioate-   N,N-Di(methoxyethyl)ammonium nonenoate-   N,N-Di(methoxyethyl)ammonium decanoate-   N,N-Di(methoxyethyl)ammonium decanedioate-   N,N-Di(methoxyethyl)ammonium decenoate-   N,N-Di(methoxyethyl)ammonium undecanoate-   N,N-Di(methoxyethyl)ammonium undecanedioate-   N,N-Di(methoxyethyl)ammonium undecenoate-   N,N-Di(methoxyethyl)ammonium dodecanoate-   N,N-Di(methoxyethyl)ammonium dodecanedicarboxylate-   N,N-Di(methoxyethyl)ammonium dodecenecarboxylate-   N,N-Di(methoxyethyl)ammonium cyclohexanecarboxylate-   N,N-Di(methoxyethyl)ammonium cyclohexenecarboxylate-   N,N-Di(methoxyethyl)ammonium phenoxide-   N,N-Di(methoxyethyl)ammonium benzoate-   N,N-Di(methoxyethyl)ammonium benezenedicarboxylate-   N,N-Di(methoxyethyl)ammonium benzenetricarboxylate-   N,N-Di(methoxyethyl)ammonium benzenetetracarboxylate-   N,N-Di(methoxyethyl)ammonium chlorobenzoate-   N,N-Di(methoxyethyl)ammonium fluorobenzoate-   N,N-Di(methoxyethyl)ammonium pentachlorobenzoate-   N,N-Di(methoxyethyl)ammonium pentafluorobenzoate-   N,N-Di(methoxyethyl)ammonium salicylate-   N,N-Di(methoxyethyl)ammonium glycolate-   N,N-Di(methoxyethyl)ammonium lactate-   N,N-Di(methoxyethyl)ammonium pantothenate-   N,N-Di(methoxyethyl)ammonium tartrate-   N,N-Di(methoxyethyl)ammonium hydrogen tartrate-   N,N-Di(methoxyethyl)ammonium mandelate-   N,N-Di(methoxyethyl)ammonium crotonate-   N,N-Di(methoxyethyl)ammonium malate-   N,N-Di(methoxyethyl)ammonium pyruvate-   N,N-Di(methoxyethyl)ammonium succinate-   N,N-Di(methoxyethyl)ammonium citrate-   N,N-Di(methoxyethyl)ammonium fumarate-   N,N-Di(methoxyethyl)ammonium phenylacetate-   N,N-Di(methoxyethyl)ammonium oxalate-   N,N-Di(methoxyethyl)ammonium bis(trifluoromethylsulphonyl)imide-   N,N-Di(methoxyethyl)ammonium carbonate-   N,N-Di(methoxyethyl)ammonium hydrogen carbonate-   N,N-Di(methoxyethyl)ammonium sulphate-   N,N-Di(methoxyethyl)ammonium hydrogen sulphate-   N,N-Di(methoxyethyl)ammonium phosphate-   N,N-Di(methoxyethyl)ammonium hydrogen phosphate-   N,N-Di(methoxyethyl)ammonium dihydrogen phosphate-   N,N-Di(methoxyethyl)ammonium methanesulphonate-   N,N-Di(methoxyethyl)ammonium trifluoromethanesulphonate-   N,N-Di(methoxyethyl)ammonium ethylenediaminetetraacetate-   N,N-Di(methoxyethyl)ammonium hexafluorophosphate-   N,N-Di(methoxyethyl)ammonium tetrafluoroborate-   N,N-Di(methoxyethyl)ammonium trifluoroacetate-   N,N-Di(methoxyethyl)ammonium pentafluoropropanoate-   N,N-Di(methoxyethyl)ammonium heptafluorobutanoate-   N,N-Di(methoxyethyl)ammonium phosphoenolpyruvate-   N,N-Di(methoxyethyl)ammonium nicotinamide adenine dinucleotide    phosphate-   N,N-Di(methoxyethyl)ammonium adenosinephosphate-   N,N-Di(methoxyethyl)ammonium adenosine diphosphate-   N,N-Di(methoxyethyl)ammonium adenosine triphosphate-   N,N-Di(methoxyethyl)ammonium oxyniacate-   N,N-Di(methoxyethyl)ammonium nitrate-   N,N-Di(methoxyethyl)ammonium nitrite-   1-(3-Hydroxypropyl)putrescinium chloride-   1-(3-Hydroxypropyl)putrescinium bromide-   1-(3-Hydroxypropyl)putrescinium iodide-   1-(3-Hydroxypropyl)putrescinium formate-   1-(3-Hydroxypropyl)putrescinium acetate-   1-(3-Hydroxypropyl)putrescinium propanoate-   1-(3-Hydroxypropyl)putrescinium propanedioate-   1-(3-Hydroxypropyl)putrescinium butanoate-   1-(3-Hydroxypropyl)putrescinium butenoate-   1-(3-Hydroxypropyl)putrescinium butanedioate-   1-(3-Hydroxypropyl)putrescinium pentanoate-   1-(3-Hydroxypropyl)putrescinium pentanedioate-   1-(3-Hydroxypropyl)putrescinium pentenoate-   1-(3-Hydroxypropyl)putrescinium hexanoate-   1-(3-Hydroxypropyl)putrescinium hexenoate-   1-(3-Hydroxypropyl)putrescinium heptanoate-   1-(3-Hydroxypropyl)putrescinium heptanedioate-   1-(3-Hydroxypropyl)putrescinium heptenoate-   1-(3-Hydroxypropyl)putrescinium octanoate-   1-(3-Hydroxypropyl)putrescinium octanedioate-   1-(3-Hydroxypropyl)putrescinium octenoate-   1-(3-Hydroxypropyl)putrescinium nonanoate-   1-(3-Hydroxypropyl)putrescinium nonanedioate-   1-(3-Hydroxypropyl)putrescinium nonenoate-   1-(3-Hydroxypropyl)putrescinium decanoate-   1-(3-Hydroxypropyl)putrescinium decanedioate-   1-(3-Hydroxypropyl)putrescinium decenoate-   1-(3-Hydroxypropyl)putrescinium undecanoate-   1-(3-Hydroxypropyl)putrescinium undecanedioate-   1-(3-Hydroxypropyl)putrescinium undecenoate-   1-(3-Hydroxypropyl)putrescinium dodecanoate-   1-(3-Hydroxypropyl)putrescinium dodecanedicarboxylate-   1-(3-Hydroxypropyl)putrescinium dodecenecarboxylate-   1-(3-Hydroxypropyl)putrescinium cyclohexanecarboxylate-   1-(3-Hydroxypropyl)putrescinium cyclohexenecarboxylate-   1-(3-Hydroxypropyl)putrescinium phenoxide-   1-(3-Hydroxypropyl)putrescinium benzoate-   1-(3-Hydroxypropyl)putrescinium benezenedicarboxylate-   1-(3-Hydroxypropyl)putrescinium benzenetricarboxylate-   1-(3-Hydroxypropyl)putrescinium benzenetetracarboxylate-   1-(3-Hydroxypropyl)putrescinium chlorobenzoate-   1-(3-Hydroxypropyl)putrescinium fluorobenzoate-   1-(3-Hydroxypropyl)putrescinium pentachlorobenzoate-   1-(3-Hydroxypropyl)putrescinium pentafluorobenzoate-   1-(3-Hydroxypropyl)putrescinium salicylate-   1-(3-Hydroxypropyl)putrescinium glycolate-   1-(3-Hydroxypropyl)putrescinium lactate-   1-(3-Hydroxypropyl)putrescinium pantothenate-   1-(3-Hydroxypropyl)putrescinium tartrate-   1-(3-Hydroxypropyl)putrescinium hydrogen tartrate-   1-(3-Hydroxypropyl)putrescinium mandelate-   1-(3-Hydroxypropyl)putrescinium crotonate-   1-(3-Hydroxypropyl)putrescinium malate-   1-(3-Hydroxypropyl)putrescinium pyruvate-   1-(3-Hydroxypropyl)putrescinium succinate-   1-(3-Hydroxypropyl)putrescinium citrate-   1-(3-Hydroxypropyl)putrescinium fumarate-   1-(3-Hydroxypropyl)putrescinium phenylacetate-   1-(3-Hydroxypropyl)putrescinium oxalate-   1-(3-Hydroxypropyl)putrescinium bis(trifluoromethylsulphonyl)imide-   1-(3-Hydroxypropyl)putrescinium methanesulphonate-   1-(3-Hydroxypropyl)putrescinium trifluoromethanesulphonate-   1-(3-Hydroxypropyl)putrescinium hexafluorophosphate-   1-(3-Hydroxypropyl)putrescinium tetrafluoroborate-   1-(3-Hydroxypropyl)putrescinium trifluoroacetate-   1-(3-Hydroxypropyl)putrescinium pentafluoropropanoate-   1-(3-Hydroxypropyl)putrescinium heptafluorobutanoate-   1-(3-Hydroxypropyl)putrescinium phosphoenolpyruvate-   1-(3-Hydroxypropyl)putrescinium nicotinamide adenine dinucleotide    phosphate-   1-(3-Hydroxypropyl)putrescinium adenosinephosphate-   1-(3-Hydroxypropyl)putrescinium adenosine diphosphate-   1-(3-Hydroxypropyl)putrescinium adenosine triphosphate-   1-(3-Hydroxypropyl)putrescinium carbonate-   1-(3-Hydroxypropyl)putrescinium hydrogen carbonate-   1-(3-Hydroxypropyl)putrescinium sulphate-   1-(3-Hydroxypropyl)putrescinium hydrogen sulphate-   1-(3-Hydroxypropyl)putrescinium phosphate-   1-(3-Hydroxypropyl)putrescinium hydrogen phosphate-   1-(3-Hydroxypropyl)putrescinium dihydrogen phosphate-   1-(3-Hydroxypropyl)putrescinium nitrate-   1-(3-Hydroxypropyl)putrescinium nitrite

In one class of compounds, the invention includes the proviso that theionic liquid is not ethylammonium nitrate or diethanolammonium chloride.In a further class of compounds, the invention includes the proviso thatthe ionic liquid is not a N-protonated pyridimium or pyrrolidinium salt.

According to a further aspect, the present invention provides a processfor the preparation of an ionic liquid according to the invention, theprocess comprising the steps of:

-   -   i.) providing an organic primary, secondary or tertiary amine;        and    -   ii.) neutralising the compound in (i) with an acid.

The process according to the invention may comprise the steps of:

-   -   i.) providing a nitrogen-containing compound of the formula (II)        NRR′R″   (II)    -   in which R, R′ and R″ have the meaning defined herein; and    -   ii.) neutralising the compound in (i) with an acid.

The process of the present invention provides an economical route to themanufacture of ionic liquids since the process involves only a singlestep and uses starting materials that are generally readily available.

During the process of the invention, the nitrogen atom of the primary,secondary or tertiary amine is protonated to provide a protonatedammonium ion.

Preferably, the acid includes an anion as defined herein.

Preferably the acid anion comprises a halogenated inorganic anion,nitrate, sulphate, carbonate, sulphonate or carboxylate.

The invention also encompasses compounds of formula (II) and their usein the preparation of one or more ionic liquids.

The invention further provides the use of a cation as defined in theionic liquids of the present invention in a solvent for enzyme-catalysedreactions. Further provided is the use of an ionic liquid according tothe present invention as a solvent for enzyme-catalysed reactions.

The use of ionic liquids in certain biological and/or chemical reactionshas several advantages over traditional aqueous solutions. Ionic liquidshave an ability to dissolve a wide range of inorganic, organic,polymeric and biological materials, often to a very high concentration.They have a wide liquid range, allowing both high and low temperatureprocesses to be carried out in the same solvent. They do not elicitsolvolysis phenomena and most stabilise short-lived reactiveintermediates. There are no pH effects in the solvents and there ispractically zero vapour pressure over much of the liquid range. Ionicliquids also exhibit excellent electrical and thermal conductivitywhilst being non-flammable, recyclable and generally of low toxicity.

The invention further provides the use of an ionic liquid, or of acation as defined in an ionic liquid, according to the present inventionin a solvent for organic synthesis, matrixes in matrix-assisted laserdesorption/ionisation (MALDI) mass spectrometry, solvent extraction (e.gto remove desired components from an immiscible liquid or solid) or gaschromatography, catalysis, liquefaction, nuclear fuel reprocessing, fuelcells, electrochemical applications, pervaporation, drug delivery,lubrication, hydraulic fluids, adhesives, sensors, biocides andchromatographic media.

Further provided is a method for carrying out an enzyme-catalysedreaction comprising

-   -   i.) providing a liquid reaction medium which comprises an ionic        liquid according to the present invention;    -   ii.) providing in the liquid reaction medium an enzyme and a        substrate for the enzyme; and    -   iii.) allowing reaction of the substrate to occur.

Further provided is a method for the synthesis of one or more organiccompounds, the method comprising carrying out an organic synthesisreaction in an ionic liquid according to the present invention.

Throughout the description and claims of this specification, the words“comprise” and “contain” and variations of the words, for example“comprising” and “comprises”, means “including but not limited to”, andis not intended to (and does not) exclude other moieties, additives,components, integers or steps.

Throughout the description and claims of this specification, thesingular encompasses the plural unless the context otherwise requires.In particular, where the indefinite article is used, the specificationis to be understood as contemplating plurality as well as singularity,unless the context requires otherwise.

Features, integers, characteristics, compounds, chemical moieties orgroups described in conjunction with a particular aspect, embodiment orexample of the invention are to be understood to be applicable to anyother aspect, embodiment or example described herein unless incompatibletherewith.

The invention will now be described by way of the following,non-limiting examples:

MATERIALS AND METHODS

Preparation of Ammonium-based Ionic Liquids Bearing One or MoreAmmoniacal Protons

The requisite stoichiometric equivalents of the parent amine andcomplementary acid were dissolved independently in water, methanol orethanol to give solutions of equal concentrations. Equal volumes ofthese two solutions were mixed together in a flask, with stirring andcooling, at a rate sufficiently slow as to prevent the temperature ofthe reaction from exceeding 60° C. When neutralization was complete, theexcess solvent was removed in vacuo, at temperatures not exceeding 60°C. The product was then freeze-dried, analysed and stored in adesiccated condition.

Preparation of N,N-dimethylethanolammonium glycolate

Alcoholic solutions of N,N-dimethyethanolamine (100.00 mL, 2.000Mconcentration) and glycolic acid (100.00 mL, 2.000M concentration) weregradually mixed together in a 500 mL round-bottomed flask, with externalcooling and stirring. After completion of the neutralisation reaction,the cold alcoholic solution was filtered, transferred to a clean flaskand the solvent was removed on a rotary evaporator. The reaction productwas frozen in liquid nitrogen and lyophilised in vacuo, being graduallypermitted to rise to room temperature, to yield 32.85 g (99%) of a paleyellow liquid, water content <100 ppm by Karl Fischer titration,purity >99.9% by ion chromatography. The product was analysed byelemental analysis and by infra-red, ultra-violet/visible and nuclearmagnetic resonance spectroscopy and was stored over anhydrous calciumchloride in a vacuum desiccator.

-   FT-IR (cm⁻¹): 1591, 1076, 1358, 687, 993, 1468, 909, 1255, 881,    1154, 1171, 3240, 2870, 2484, 1745-   UV/vis λ_(max) (nm): 234-   E^(N) _(T) (Reichardt): 0.912-   Density (g cm ⁻³): 1.146    Preparation of N-butyldiethanolammonium    bis(trifluoromethylsulphonyl)imide

To an alcoholic solution of N-butyldiethanolamine (100.00 mL, 2.000Mconcentration) in a 500 mL round-bottomed flask was gradually added56.232 g bis(trifluoromethylsulphonyl)imide, with vigorous stirring andexternal cooling, over a period of 30 minutes. After completion of thereaction, the solution was filtered and the solvent was removed invacuo. The product was dried as above to yield 87.2 g (98%) of a paleyellow liquid, water content <100 ppm by Karl Fischer titration,purity >98% by ion chromatography. The product was analysed and storedas previously described.

-   FT-IR (cm⁻¹):1051, 1132, 1181, 1347, 741, 791, 764, 880, 960, 1461,    2967, 3523, 2941, 2880, 3138, 1632-   UV/vis λ_(max) (nm): 304-   E^(N) _(T) (Reichardt): 0.994-   Density (g cm⁻³): 1.343

APPLICATIONS

Enzyme-catalysed Reaction in N,N-dimethylethanolammonium glycolate

Alcohol dehydrogenase: Methanol (50 μL) was dissolved in the ionicliquid (6 mL) with a net water content of <100 ppm by Karl Fischertitration. Nicotinamide adenine dinucleotide (100 mg) was added alongwith lyophilised Saccharomyces cerevisiae alcohol dehydrogenase (1 mg).The reaction vessel was sealed and incubated at 30° C. for 24 hours,with vigorous shaking being maintained throughout. Samples (1 mL) wereextracted at time points of 0, 2, 4, 8, 12 and 24 hours and wereanalysed by means of the chromotropic acid assay. The absorbance of theanalyte samples at 560 nm was measured against enzyme-free standards andcorrelated with the concentration of formaldehyde by comparison with astandard curve. The accumulation of formaldehyde was observed up to anequilibrium concentration of 20+/−2 mM.

Biodegradation of N,N-dimethylethanolammonium glycolate

N,N-Dimethylethanolammonium glycolate (5 mM) was used as sole nitrogenand carbon source for the selective enrichment of a mixed community ofsoil micro-organisms collected from waste ground. Individual organismswere isolated from the mixed culture and were screened for theircapability to metabolise the ionic liquid at varying concentrations inaqueous phosphate buffer. Experiments were performed in Erlenmeyerflasks at 30° C., with shaking at 110 rpm. Degradation was monitoredusing ion chromatography. 5 mM Ionic liquid was readily degraded (>98%removal) within 48 hours, the final nitrogenous metabolite beingammonia.

1-31. (canceled)
 32. An ionic liquid comprising an anion and a cationcharacterized in that the cation is a secondary or tertiarynitrogen-containing cation of the formula (I)N⁺HRR′R″  (I) wherein: R is a hydrocarbyl substituted with one or moresubstituents selected from the group consisting of nitrile, nitro,amino, or other nitrogen-containing functional group; thiol; alkylthio;sulphonyl; thiocyanate; isothiocyanate; azido; hydrazine; halogen; alkyloptionally having one or more ether or thioether linkages; alkoxy;alkenyl; hydroxyl; carbonyl; carboxyl; boronate; silyl; and substitutedamino; R′ is a hydrocarbyl optionally substituted with one or moresubstituents selected from the group consisting of nitrile, nitro,amino, or other nitrogen-containing functional group; thiol; alkylthio;sulphonyl; thiocyanate; isothiocyanate; azido; hydrazine; halogen; alkyloptionally having one or more ether or thioether linkages; alkoxy;alkenyl; hydroxyl; carbonyl; carboxyl; boronate; silyl; and substitutedamino; R″ is H or R′; any two or three of R, R′ and R″ may optionally bejoined together with the N to form a heterocyclic group, provided theheterocyclic group is not heteroaryl; the ionic liquid has a meltingpoint below 25° C. and contains less than 1% water; and the ionic liquidis not diethanolammonium chloride.
 33. The ionic liquid of claim 32,wherein R′ and R″ are different and R″ is not H.
 34. The ionic liquid ofclaim 32, wherein R is substituted with a moiety selected from the groupconsisting of alkenyl, hydroxyl, amino, thio, carbonyl and carboxyl. 35.The ionic liquid of claim 34, wherein R is substituted with a hydroxylor amino.
 36. The ionic liquid of claim 35, wherein R is a hydroxyalkylhaving 1, 2, 3, 4, 5 or 6 C atoms.
 37. The ionic liquid of claim 36,wherein the hydroxyalkyl has a hydroxyl moiety on its free, terminalcarbon.
 38. The ionic liquid of claim 36, wherein R is a polyol having 2to 6 C atoms.
 39. The ionic liquid of claim 38, wherein R is a diol,triol or tetra-ol.
 40. The ionic liquid of claim 32, wherein the cationis an N-methylethanolammonium, N,N-dimethylethanolammonium,diethanolammonium, N-alkyldiethanolammonium,N,N-di(alkoxyalkyl)ammonium, triethanolammonium,N-butyldiethanolammonium, N-(3-hydroxypropyl)putrescinium orN-(3-hydroxypropyl)-N-methylcyclohexylammonium ion.
 41. The ionic liquidof claim 40, wherein the cation is an N-methylethanolammonium,N,N-dimethylethanolammonium, diethanolammonium,N-alkyldiethanolammonium, N,N-di(alkoxyalkyl)ammonium ortriethanolammonium ion.
 42. The ionic liquid of claim 41, wherein thecation is an N-methylethanolammonium, N,N-dimethylethanolammonium,N,N-di(methoxyethyl)ammonium or N-butyldiethanolammonium ion.
 43. Theionic liquid of claim 32, wherein R is an aminoalkyl having 2 to 8 Catoms.
 44. The ionic liquid of claim 43, wherein the aminoalkyl is a di-or tri-aminoalkyl.
 45. The ionic liquid of claim 32, wherein R isputrescine, piperidine or tropine.
 46. The ionic liquid of claim 40,wherein the cation is selected from the group consisting ofdiethanolammonium, N-butyldiethanolammonium, N-methylethanolammonium,N,N-dimethylethanolammonium, N-(3-hydroxypropyl)putrescinium andN-(3-hydroxypropyl)-N-methylcyclohexylammonium ions.
 47. The ionicliquid of claim 46, wherein the cation is an N-butyldiethanolammonium,N-methylethanolammonium, N,N-dimethylethanolammonium,N-(3-hydroxypropyl)putrescinium orN-(3-hydroxypropyl)-N-methylcyclohexylammonium ion.
 48. The ionic liquidof claim 32, wherein R is substituted with a hydroxyl or alkoxyl. 49.The ionic liquid of claim 32, wherein the anion is selected from thegroup consisting of halogenated inorganic anions, nitrates, sulphates,phosphates, carbonates, sulphonates and carboxylates.
 50. The ionicliquid of claim 49, wherein the sulphonates and carboxylates arealkylsulphonates and alkylcarboxylates respectively.
 51. The ionicliquid of claim 50, wherein the alkyl portion of the alkylsulphonate oralkylcarboxylate is optionally substituted at any position with alkenyl,alkoxy, alkeneoxy, aryl, arylalkyl, aryloxy, amino, aminoalkyl, thio,thioalkyl, hydroxyl, hydroxyalkyl, carbonyl, oxoalkyl, carboxyl,carboxyalkyl or halide.
 52. The ionic liquid of claim 32, wherein theanion is selected from the group consisting ofbis(trifluoromethylsulphonyl)imide, carbonate, hydrogen carbonate,sulphate, hydrogen sulphate, silicate, phosphate, hydrogen phosphate,dihydrogen phosphate, metaphosphate, methanesulphonate,trifluoromethanesulphonate, ethylenediaminetetraacetate, chloride,bromide, iodide, hexafluorophosphate, tetrafluoroborate,trifluoroacetate, pentafluoropropanoate, heptafluorobutanoate, oxalate,formate, acetate, propanoate, butanoate, pentanoate, hexanoate,heptanoate, octanoate, nonanoate, decanoate, benzoate,benezenedicarboxylate, benzenetricarboxylate, benzenetetracarboxylate,chlorobenzoate, fluorobenzoate, pentachlorobenzoate, pentafluorobenzoatesalicylate, glycolate lactate, pantothenate, tartrate, hydrogentartrate, mandelate, crotonate, malate, pyruvate, succinate, citrate,fumarate and phenylacetate.
 53. The ionic liquid of claim 52, whereinthe anion is an organic carboxylate.
 54. The ionic liquid of claim 32,wherein the ionic liquid is selected from the group consisting of:diethanolammonium bromide; diethanolammonium iodide; diethanolammoniumformate; diethanolammonium acetate; diethanolammonium propanoate;diethanolammonium propanedioate; diethanolammonium butanoate;diethanolammonium butenoate; diethanolammonium butanedioate;diethanolammonium pentanoate; diethanolammonium pentanedioate;diethanolammonium pentenoate; diethanolammonium hexanoate;diethanolammonium hexanedioate; diethanolammonium hexenoate;diethanolammonium heptanoate; diethanolammonium heptanedioate;diethanolammonium heptenoate; diethanolammonium octanoate;diethanolammonium octanedioate; diethanolammonium octenoate;diethanolammonium nonanoate; diethanolammonium nonanedioate;diethanolammonium nonenoate; diethanolammonium decanoate;diethanolammonium decanedioate; diethanolammonium decenoate;diethanolammonium undecanoate; diethanolammonium undecanedioate;diethanolammonium undecenoate; diethanolammonium dodecanoate;diethanolammonium dodecanedicarboxylate; diethanolammoniumdodecenecarboxylate; diethanolammonium cyclohexanecarboxylate;diethanolammonium cyclohexenecarboxylate; diethanolammonium phenoxide;diethanolammonium benzoate; diethanolammonium benezenedicarboxylate;diethanolammonium benzenetricarboxylate; diethanolammoniumbenzenetetracarboxylate; diethanolammonium chlorobenzoate;diethanolammonium fluorobenzoate; diethanolammonium pentachlorobenzoate;diethanolammonium pentafluorobenzoate; diethanolammonium salicylate;diethanolammonium glycolate; diethanolammonium lactate;diethanolammonium pantothenate; diethanolammonium tartrate;diethanolammonium hydrogen tartrate; diethanolammonium mandelate;diethanolammonium crotonate; diethanolammonium malate; diethanolammoniumpyruvate; diethanolammonium succinate; diethanolammonium citrate;diethanolammonium fumarate; diethanolammonium phenylacetate;diethanolammonium oxalate; diethanolammoniumbis(trifluoromethylsulphonyl)imide; diethanolammonium carbonate;diethanolammonium hydrogen carbonate; diethanolammonium phosphate;diethanolammonium hydrogen phosphate; diethanolammonium dihydrogenphosphate; diethanolammonium methanesulphonate; diethanolammoniumtrifluoromethanesulphonate; diethanolammoniumethylenediaminetetraacetate; diethanolammonium hexafluorophosphate;diethanolammonium tetrafluoroborate; diethanolammonium trifluoroacetate;diethanolammonium pentafluoropropanoate; diethanolammoniumheptafluorobutanoate; diethanolammonium phosphoenolpyruvate;diethanolammonium nicotinamide adenine dinucleotide phosphate;diethanolammonium adenosinephosphate; diethanolammonium adenosinediphosphate; diethanolammonium adenosine triphosphate; diethanolammoniumoxyniacate; diethanolammonium nitrate; diethanolammonium nitrite;N-butyldiethanolammonium chloride; N-butyldiethanolammonium bromide;N-butyldiethanolammonium iodide; N-butyldiethanolammonium formate;N-butyldiethanolammonium acetate; N-butyldiethanolammonium propanoate;N-butyldiethanolammonium propanedioate; N-butyldiethanolammoniumbutanoate; N-butyldiethanolammonium butenoate; N-butyldiethanolammoniumbutanedioate; N-butyldiethanolammonium pentanoate;N-butyldiethanolammonium pentanedioate; N-butyldiethanolammoniumpentenoate; N-butyldiethanolammonium hexanoate; N-butyldiethanolammoniumhexenoate; N-butyldiethanolammonium heptanoate; N-butyldiethanolammoniumheptanedioate; N-butyldiethanolammonium heptenoate;N-butyldiethanolammonium octanoate; N-butyldiethanolammoniumoctanedioate; N-butyldiethanolammonium octenoate;N-butyldiethanolammonium nonanoate; N-butyldiethanolammoniumnonanedioate; N-butyldiethanolammonium nonenoate;N-butyldiethanolammonium decanoate; N-butyldiethanolammoniumdecanedioate; N-butyldiethanolammonium decenoate;N-butyldiethanolammonium undecanoate; N-butyldiethanolammoniumundecanedioate; N-butyldiethanolammonium undecenoate;N-butyldiethanolammonium dodecanoate; N-butyldiethanolammoniumdodecanedicarboxylate; N-butyldiethanolammonium dodecenecarboxylate;N-butyldiethanolammonium cyclohexanecarboxylate;N-butyldiethanolammonium cyclohexenecarboxylate;N-butyldiethanolammonium phenoxide; N-butyldiethanolammonium benzoate;N-butyldiethanolammonium benezenedicarboxylate; N-butyldiethanolammoniumbenzenetricarboxylate; N-butyldiethanolammonium benzenetetracarboxylate;N-butyldiethanolammonium chlorobenzoate; N-butyldiethanolammoniumfluorobenzoate; N-butyldiethanolammonium pentachlorobenzoate;N-butyldiethanolammonium pentafluorobenzoate; N-butyldiethanolammoniumsalicylate; N-butyldiethanolammonium glycolate; N-butyldiethanolammoniumlactate; N-butyldiethanolammonium pantothenate; N-butyldiethanolammoniumtartrate; N-butyldiethanolammonium hydrogen tartrate;N-butyldiethanolammonium mandelate; N-butyldiethanolammonium crotonate;N-butyldiethanolammonium malate; N-butyldiethanolammonium pyruvate;N-butyldiethanolammonium succinate; N-butyldiethanolammonium citrate;N-butyldiethanolammonium fumarate; N-butyldiethanolammoniumphenylacetate; N-butyldiethanolammonium oxalate;N-butyldiethanolammonium bis(trifluoromethylsulphonyl)imide;N-butyldiethanolammonium carbonate; N-butyldiethanolammonium hydrogencarbonate; N-butyldiethanolammonium sulphate; N-butyldiethanolammoniumhydrogen sulphate; N-butyldiethanolammonium phosphate;N-butyldiethanolammonium hydrogen phosphate; N-butyldiethanolammoniumdihydrogen phosphate; N-butyldiethanolammonium methanesulphonate;N-butyldiethanolammonium trifluoromethanesulphonate;N-butyldiethanolammonium ethylenediaminetetraacetate;N-butyldiethanolammonium hexafluorophosphate; N-butyldiethanolammoniumtetrafluoroborate; N-butyldiethanolammonium trifluoroacetate;N-butyldiethanolammonium pentafluoropropanoate; N-butyldiethanolammoniumheptafluorobutanoate; N-butyldiethanolammonium phosphoenolpyruvate;N-butyldiethanolammonium nicotinamide adenine dinucleotide phosphate;N-butyldiethanolammonium adenosinephosphate; N-butyldiethanolammoniumadenosine diphosphate; N-butyldiethanolammonium adenosine triphosphate;N-butyldiethanolammonium oxyniacate; N-butyldiethanolammonium nitrate;N-butyldiethanolammonium nitrite; N,N-dimethylethanolammonium bromide;N,N-dimethylethanolammonium iodide; N,N-dimethylethanolammonium formate;N,N-dimethylethanolammonium acetate; N,N-dimethylethanolammoniumpropanoate; N,N-dimethylethanolammonium propanedioate;N,N-dimethylethanolammonium butanoate; N,N-dimethylethanolammoniumbutenoate; N,N-dimethylethanolammonium butanedioate;N,N-dimethylethanolammonium pentanoate; N,N-dimethylethanolammoniumpentanedioate; N,N-dimethylethanolammonium pentenoate;N,N-dimethylethanolammonium hexanoate; N,N-dimethylethanolammoniumhexenoate; N,N-dimethylethanolammonium heptanoate;N,N-dimethylethanolammonium heptanedioate; N,N-dimethylethanolammoniumheptenoate; N,N-dimethylethanolammonium octanoate;N,N-dimethylethanolammonium octanedioate; N,N-dimethylethanolammoniumoctenoate; N,N-dimethylethanolammonium nonanoate;N,N-dimethylethanolammonium nonanedioate; N,N-dimethylethanolammoniumnonenoate; N,N-dimethylethanolammonium decanoate;N,N-dimethylethanolammonium decanedioate; N,N-dimethylethanolammoniumdecenoate; N,N-dimethylethanolammonium undecanoate;N,N-dimethylethanolammonium undecanedioate; N,N-dimethylethanolammoniumundecenoate; N,N-dimethylethanolammonium dodecanoate;N,N-dimethylethanolammonium dodecanedicarboxylate;N,N-dimethylethanolammonium dodecenecarboxylate;N,N-dimethylethanolammonium cyclohexanecarboxylate;N,N-dimethylethanolammonium cyclohexenecarboxylate;N,N-dimethylethanolammonium phenoxide; N,N-dimethylethanolammoniumbenzoate; N,N-dimethylethanolammonium benezenedicarboxylate;N,N-dimethylethanolammonium benzenetricarboxylate;N,N-dimethylethanolammonium benzenetetracarboxylate;N,N-dimethylethanolammonium chlorobenzoate; N,N-dimethylethanolammoniumfluorobenzoate; N,N-dimethylethanolammonium pentachlorobenzoate;N,N-dimethylethanolammonium pentafluorobenzoate;N,N-dimethylethanolammonium salicylate; N,N-dimethylethanolammoniumglycolate; N,N-dimethylethanolammonium lactate;N,N-dimethylethanolammonium pantothenate; N,N-dimethylethanolammoniumtartrate; N,N-dimethylethanolammonium hydrogen tartrate;N,N-dimethylethanolammonium mandelate; N,N-dimethylethanolammoniumcrotonate; N,N-dimethylethanolammonium malate;N,N-dimethylethanolammonium pyruvate; N,N-dimethylethanolammoniumsuccinate; N,N-dimethylethanolammonium citrate;N,N-dimethylethanolammonium fumarate; N,N-dimethylethanolammoniumphenylacetate; N,N-dimethylethanolammonium oxalate;N,N-dimethylethanolammonium bis(trifluoromethylsulphonyl)imide;N,N-dimethylethanolammonium carbonate; N,N-dimethylethanolammoniumhydrogen carbonate; N,N-dimethylethanolammonium sulphate;N,N-dimethylethanolammonium hydrogen sulphate;N,N-dimethylethanolammonium phosphate; N,N-dimethylethanolammoniumhydrogen phosphate; N,N-dimethylethanolammonium dihydrogen phosphate;N,N-dimethylethanolammonium methanesulphonate;N,N-dimethylethanolammonium trifluoromethanesulphonate;N,N-dimethylethanolammonium ethylenediaminetetraacetate;N,N-dimethylethanolammonium hexafluorophosphate;N,N-dimethylethanolammonium tetrafluoroborate;N,N-dimethylethanolammonium trifluoroacetate;N,N-dimethylethanolammonium pentafluoropropanoate;N,N-dimethylethanolammonium heptafluorobutanoate;N,N-dimethylethanolammonium phosphoenolpyruvate;N,N-dimethylethanolammonium nicotinamide adenine dinucleotide phosphate;N,N-dimethylethanolammonium adenosinephosphate;N,N-dimethylethanolammonium adenosine diphosphate;N,N-dimethylethanolammonium adenosine triphosphate;N,N-dimethylethanolammonium oxyniacate; N,N-dimethylethanolammoniumnitrate; N,N-dimethylethanolammonium nitrite; N-methylethanolammoniumbromide; N-methylethanolammonium iodide; N-methylethanolammoniumformate; N-methylethanolammonium acetate; N-methylethanolammoniumpropanoate; N-methylethanolammonium propanedioate;N-methylethanolammonium butanoate; N-methylethanolammonium butenoate;N-methylethanolammonium butanedioate; N-methylethanolammoniumpentanoate; N-methylethanolammonium pentanedioate;N-methylethanolammonium pentenoate; N-methylethanolammonium hexanoate;N-methylethanolammonium hexenoate; N-methylethanolammonium heptanoate;N-methylethanolammonium heptanedioate; N-methylethanolammoniumheptenoate; N-methylethanolammonium octanoate; N-methylethanolammoniumoctanedioate; N-methylethanolammonium octenoate; N-methylethanolammoniumnonanoate; N-methylethanolammonium nonanedioate; N-methylethanolammoniumnonenoate; N-methylethanolammonium decanoate; N-methylethanolammoniumdecanedioate; N-methylethanolammonium decenoate; N-methylethanolammoniumundecanoate; N-methylethanolammonium undecanedioate;N-methylethanolammonium undecenoate; N-methylethanolammoniumdodecanoate; N-methylethanolammonium dodecanedicarboxylate;N-methylethanolammonium dodecenecarboxylate; N-methylethanolammoniumcyclohexanecarboxylate; N-methylethanolammonium cyclohexenecarboxylate;N-methylethanolammonium phenoxide; N-methylethanolammonium benzoate;N-methylethanolammonium benezenedicarboxylate; N-methylethanolammoniumbenzenetricarboxylate; N-methylethanolammonium benzenetetracarboxylate;N-methylethanolammonium chlorobenzoate; N-methylethanolammoniumfluorobenzoate; N-methylethanolammonium pentachlorobenzoate;N-methylethanolammonium pentafluorobenzoate; N-methylethanolammoniumsalicylate; N-methylethanolammonium glycolate; N-methylethanolammoniumlactate; N-methylethanolammonium pantothenate; N-methylethanolammoniumtartrate; N-methylethanolammonium hydrogen tartrate;N-methylethanolammonium mandelate; N-methylethanolammonium crotonate;N-methylethanolammonium malate; N-methylethanolammonium pyruvate;N-methylethanolammonium succinate; N-methylethanolammonium citrate;N-methylethanolammonium fumarate; N-methylethanolammonium phenylacetate;N-methylethanolammonium oxalate; N-methylethanolammoniumbis(trifluoromethylsulphonyl)imide; N-methylethanolammonium carbonate;N-methylethanolammonium hydrogen carbonate; N-methylethanolammoniumsulphate; N-methylethanolammonium hydrogen sulphate;N-methylethanolammonium phosphate; N-methylethanolammonium hydrogenphosphate; N-methylethanolammonium dihydrogen phosphate;N-methylethanolammonium methanesulphonate; N-methylethanolammoniumtrifluoromethanesulphonate; N-methylethanolammoniumethylenediaminetetraacetate; N-methylethanolammoniumhexafluorophosphate; N-methylethanolammonium tetrafluoroborate;N-methylethanolammonium trifluoroacetate; N-methylethanolammoniumpentafluoropropanoate; N-methylethanolammonium heptafluorobutanoate;N-methylethanolammonium phosphoenolpyruvate; N-methylethanolammoniumnicotinamide adenine dinucleotide phosphate; N-methylethanolammoniumadenosinephosphate; N-methylethanolammonium adenosine diphosphate;N-methylethanolammonium adenosine triphosphate; N-methylethanolammoniumoxyniacate; N-methylethanolammonium nitrate; N-methylethanolammoniumnitrite; N,N-di(methoxyethyl)ammonium chloride;N,N-di(methoxyethyl)ammonium bromide; N,N-di(methoxyethyl)ammoniumiodide; N,N-di(methoxyethyl)ammonium formate;N,N-di(methoxyethyl)ammonium acetate; N,N-di(methoxyethyl)ammoniumpropanoate; N,N-di(methoxyethyl)ammonium propanedioate;N,N-di(methoxyethyl)ammonium butanoate; N,N-di(methoxyethyl)ammoniumbutenoate; N,N-di(methoxyethyl)ammonium butanedioate;N,N-di(methoxyethyl)ammonium pentanoate; N,N-di(methoxyethyl)ammoniumpentanedioate; N,N-di(methoxyethyl)ammonium pentenoate;N,N-di(methoxyethyl)ammonium hexanoate; N,N-di(methoxyethyl)ammoniumhexenoate; N,N-di(methoxyethyl)ammonium heptanoate;N,N-di(methoxyethyl)ammonium heptanedioate; N,N-di(methoxyethyl)ammoniumheptenoate; N,N-di(methoxyethyl)ammonium octanoate;N,N-di(methoxyethyl)ammonium octanedioate; N,N-di(methoxyethyl)ammoniumoctenoate; N,N-di(methoxyethyl)ammonium nonanoate;N,N-di(methoxyethyl)ammonium nonanedioate; N,N-di(methoxyethyl)ammoniumnonenoate; N,N-di(methoxyethyl)ammonium decanoate;N,N-di(methoxyethyl)ammonium decanedioate; N,N-di(methoxyethyl)ammoniumdecenoate; N,N-di(methoxyethyl)ammonium undecanoate;N,N-di(methoxyethyl)ammonium undecanedioate;N,N-di(methoxyethyl)ammonium undecenoate; N,N-di(methoxyethyl)ammoniumdodecanoate; N,N-di(methoxyethyl)ammonium dodecanedicarboxylate;N,N-di(methoxyethyl)ammonium dodecenecarboxylate;N,N-di(methoxyethyl)ammonium cyclohexanecarboxylate;N,N-di(methoxyethyl)ammonium cyclohexenecarboxylate;N,N-di(methoxyethyl)ammonium phenoxide; N,N-di(methoxyethyl)ammoniumbenzoate; N,N-di(methoxyethyl)ammonium benezenedicarboxylate;N,N-di(methoxyethyl)ammonium benzenetricarboxylate;N,N-di(methoxyethyl)ammonium benzenetetracarboxylate;N,N-di(methoxyethyl)ammonium chlorobenzoate;N,N-di(methoxyethyl)ammonium fluorobenzoate;N,N-di(methoxyethyl)ammonium pentachlorobenzoate;N,N-di(methoxyethyl)ammonium pentafluorobenzoate;N,N-di(methoxyethyl)ammonium salicylate; N,N-di(methoxyethyl)ammoniumglycolate; N,N-di(methoxyethyl)ammonium lactate;N,N-di(methoxyethyl)ammonium pantothenate; N,N-di(methoxyethyl)ammoniumtartrate; N,N-di(methoxyethyl)ammonium hydrogen tartrate;N,N-di(methoxyethyl)ammonium mandelate; N,N-di(methoxyethyl)ammoniumcrotonate; N,N-di(methoxyethyl)ammonium malate;N,N-di(methoxyethyl)ammonium pyruvate; N,N-di(methoxyethyl)ammoniumsuccinate; N,N-di(methoxyethyl)ammonium citrate;N,N-di(methoxyethyl)ammonium fumarate; N,N-di(methoxyethyl)ammoniumphenylacetate; N,N-di(methoxyethyl)ammonium oxalate;N,N-di(methoxyethyl)ammonium bis(trifluoromethylsulphonyl)imide;N,N-di(methoxyethyl)ammonium carbonate; N,N-di(methoxyethyl)ammoniumhydrogen carbonate; N,N-di(methoxyethyl)ammonium sulphate;N,N-di(methoxyethyl)ammonium hydrogen sulphate;N,N-di(methoxyethyl)ammonium phosphate; N,N-di(methoxyethyl)ammoniumhydrogen phosphate; N,N-di(methoxyethyl)ammonium dihydrogen phosphate;N,N-di(methoxyethyl)ammonium methanesulphonate;N,N-di(methoxyethyl)ammonium trifluoromethanesulphonate;N,N-di(methoxyethyl)ammonium ethylenediaminetetraacetate;N,N-di(methoxyethyl)ammonium hexafluorophosphate;N,N-di(methoxyethyl)ammonium tetrafluoroborate;N,N-di(methoxyethyl)ammonium trifluoroacetate;N,N-di(methoxyethyl)ammonium pentafluoropropanoate;N,N-di(methoxyethyl)ammonium heptafluorobutanoate;N,N-di(methoxyethyl)ammonium phosphoenolpyruvate;N,N-di(methoxyethyl)ammonium nicotinamide adenine dinucleotidephosphate; N,N-di(methoxyethyl)ammonium adenosinephosphate;N,N-di(methoxyethyl)ammonium adenosine diphosphate;N,N-di(methoxyethyl)ammonium adenosine triphosphate;N,N-di(methoxyethyl)ammonium oxyniacate; N,N-di(methoxyethyl)ammoniumnitrate; N,N-di(methoxyethyl)ammonium nitritel1-(3-Hydroxypropyl)putrescinium chloride;N-(3-hydroxypropyl)putrescinium bromide; N-(3-hydroxypropyl)putresciniumiodide; N-(3-hydroxypropyl)putrescinium formate;N-(3-hydroxypropyl)putrescinium acetate; N-(3-hydroxypropyl)putresciniumpropanoate; N-(3-hydroxypropyl)putrescinium propanedioate;N-(3-hydroxypropyl)putrescinium butanoate;N-(3-hydroxypropyl)putrescinium butenoate;N-(3-hydroxypropyl)putrescinium butanedioate;N-(3-hydroxypropyl)putrescinium pentanoate;N-(3-hydroxypropyl)putrescinium pentanedioate;N-(3-hydroxypropyl)putrescinium pentenoate;N-(3-hydroxypropyl)putrescinium hexanoate;N-(3-hydroxypropyl)putrescinium hexenoate;N-(3-hydroxypropyl)putrescinium heptanoate;N-(3-hydroxypropyl)putrescinium heptanedioate;N-(3-hydroxypropyl)putrescinium heptenoate;N-(3-hydroxypropyl)putrescinium octanoate;N-(3-hydroxypropyl)putrescinium octanedioate;N-(3-hydroxypropyl)putrescinium octenoate;N-(3-hydroxypropyl)putrescinium nonanoate;N-(3-hydroxypropyl)putrescinium nonanedioate;N-(3-hydroxypropyl)putrescinium nonenoate;N-(3-hydroxypropyl)putrescinium decanoate;N-(3-hydroxypropyl)putrescinium decanedioate;N-(3-hydroxypropyl)putrescinium decenoate;N-(3-hydroxypropyl)putrescinium undecanoate;N-(3-hydroxypropyl)putrescinium undecanedioate;N-(3-hydroxypropyl)putrescinium undecenoate;N-(3-hydroxypropyl)putrescinium dodecanoate;N-(3-hydroxypropyl)putrescinium dodecanedicarboxylate;N-(3-hydroxypropyl)putrescinium dodecenecarboxylate;N-(3-hydroxypropyl)putrescinium cyclohexanecarboxylate;N-(3-hydroxypropyl)putrescinium cyclohexenecarboxylate;N-(3-hydroxypropyl)putrescinium phenoxide;N-(3-hydroxypropyl)putrescinium benzoate;N-(3-hydroxypropyl)putrescinium benezenedicarboxylate;N-(3-hydroxypropyl)putrescinium benzenetricarboxylate;N-(3-hydroxypropyl)putrescinium benzenetetracarboxyl ate;N-(3-hydroxypropyl)putrescinium chlorobenzoate;N-(3-hydroxypropyl)putrescinium fluorobenzoate;N-(3-hydroxypropyl)putrescinium pentachlorobenzoate;N-(3-hydroxypropyl)putrescinium pentafluorobenzoate;N-(3-hydroxypropyl)putrescinium salicylate;N-(3-hydroxypropyl)putrescinium glycolate;N-(3-hydroxypropyl)putrescinium lactate; N-(3-hydroxypropyl)putresciniumpantothenate; N-(3-hydroxypropyl)putrescinium tartrate;N-(3-hydroxypropyl)putrescinium hydrogen tartrate;N-(3-hydroxypropyl)putrescinium mandelate;N-(3-hydroxypropyl)putrescinium crotonate;N-(3-hydroxypropyl)putrescinium malate; N-(3-hydroxypropyl)putresciniumpyruvate; N-(3-hydroxypropyl)putrescinium succinate;N-(3-hydroxypropyl)putrescinium citrate; N-(3-hydroxypropyl)putresciniumfumarate; N-(3-hydroxypropyl)putrescinium phenylacetate;N-(3-hydroxypropyl)putrescinium oxalate; N-(3-hydroxypropyl)putresciniumbis(trifluoromethylsulphonyl)imide; N-(3-hydroxypropyl)putresciniummethanesulphonate; N-(3-hydroxypropyl)putresciniumtrifluoromethanesulphonate; N-(3-hydroxypropyl)putresciniumhexafluorophosphate; N-(3-hydroxypropyl)putrescinium tetrafluoroborate;N-(3-hydroxypropyl)putrescinium trifluoroacetate;N-(3-hydroxypropyl)putrescinium pentafluoropropanoate;N-(3-hydroxypropyl)putrescinium heptafluorobutanoate;N-(3-hydroxypropyl)putrescinium phosphoenolpyruvate;N-(3-hydroxypropyl)putrescinium nicotinamide adenine dinucleotidephosphate; N-(3-hydroxypropyl)putrescinium adenosinephosphate;N-(3-hydroxypropyl)putrescinium adenosine diphosphate;N-(3-hydroxypropyl)putrescinium adenosine triphosphate;N-(3-hydroxypropyl)putrescinium carbonate;N-(3-hydroxypropyl)putrescinium hydrogen carbonate;N-(3-hydroxypropyl)putrescinium sulphate;N-(3-hydroxypropyl)putrescinium hydrogen sulphate;N-(3-hydroxypropyl)putrescinium phosphate;N-(3-hydroxypropyl)putrescinium hydrogen phosphate;N-(3-hydroxypropyl)putrescinium dihydrogen phosphate;N-(3-hydroxypropyl)putrescinium nitrate; andN-(3-hydroxypropyl)putrescinium nitrite.
 55. A process for thepreparation of an ionic liquid of claim 32, the process comprising thesteps of: i.) providing an organic secondary or tertiary amine; and ii.)neutralizing the compound in (i) with an acid.
 56. The process of claim55, wherein the acid includes an anion comprising a halogenatedinorganic anion, nitrate, sulphate, carbonate, sulphonate orcarboxylate.
 57. A method for using the ionic liquid of claim 32 in anapplication selected from the group consisting of a solvent forenzyme-catalyzed reactions, a solvent for organic synthesis, a matrix inmatrix-assisted laser desorption/ionisation (MALDI) mass spectrometry, asolvent for extraction, catalysis or liquefaction, a nuclear fuelreprocessing medium, a fuel cell additive, an electrochemicalapplication, pervaporation, drug delivery, lubrication, hydraulics,adhesives, sensors, biocides, and chromatographic media.
 58. A methodfor carrying out an enzyme-catalyzed reaction comprising: i.) providinga liquid reaction medium which contains an ionic liquid comprising ananion and a cation wherein the cation is a primary, secondary ortertiary ammonium ion of the formula (I)N⁺HRR′R″  (I) wherein: R is a hydrocarbyl substituted with one or moresubstituents selected from the group consisting of nitrile, nitro,amino, or other nitrogen-containing functional group; thiol; alkylthio;sulphonyl; thiocyanate; isothiocyanate; azido; hydrazine; halogen; alkyloptionally having one or more ether or thioether linkages; alkoxy;alkenyl; hydroxyl; carbonyl; carboxyl; boronate; silyl; and substitutedamino; R′ and R″, which may be the same or different, are H or ahydrocarbyl optionally substituted with one or more substituentsselected from the group consisting of nitrile, nitro, amino, or othernitrogen-containing functional group; thiol; alkylthio; sulphonyl;thiocyanate; isothiocyanate; azido; hydrazine; halogen; alkyl optionallyhaving one or more ether or thioether linkages; alkoxy; alkenyl;hydroxyl; carbonyl; carboxyl; boronate; silyl; and substituted amino;and any two or three of R, R′ and R″ may be joined together with the Nto form a heterocyclic (excluding heteroaryl) group; ii.) providing inthe liquid reaction medium an enzyme and a substrate for the enzyme; andiii.) allowing reaction of the substrate to occur.
 59. The method ofclaim 58, wherein the ionic liquid is the ionic liquid of claim
 32. 60.The method of claim 58, wherein the ionic liquid is the ionic liquid ofclaim
 40. 61. The method of claim 58, wherein the ionic liquid is theionic liquid of claim 54.